A porous material adsorbent and a preparation method and application thereof

Abstract

The present application relates to the technical field of adsorbent, in particular to a porous material adsorbent and its preparation method and application. The preparation method comprises the following steps: (1) adding a ruthenium-containing substance and an organic peroxide into a first organic solvent to perform a first reaction, adding a crosslinking agent to perform a second reaction, and obtaining a precursor solution; (2) adding a second organic solvent into the precursor solution to mix, obtaining a ligand mixture; (3) adding graphene oxide into the ligand mixture to mix, obtaining an adsorbent slurry, performing solid-liquid separation, calcination and extrusion molding on the adsorbent slurry, and obtaining a porous material adsorbent. The prepared porous material adsorbent has a large specific surface area, a large pore size and a large pore volume, and has a high compressive strength. The porous material adsorbent is applied in the field of adsorption desulfurization, has a high total sulfur breakthrough sulfur capacity and a high tail gas outlet precision.

Description

Technical Field

[0001] This invention relates to the field of adsorbent technology, specifically to a porous material adsorbent, its preparation method, and its application. Background Technology

[0002] Reactive sulfur-containing substances such as sulfur, hydrogen sulfide, thiols, and sulfides have low boiling points and are chemically active. They can generally be removed using industrially common techniques. However, inactive sulfur-containing compounds such as sulfides, thiophene, benzothiophene, and dibenzothiophene are relatively stable and difficult to remove. Summary of the Invention

[0003] Therefore, the technical problem to be solved by the present invention is to overcome the defect of poor adsorption of inactive sulfur-containing compounds in the prior art, thereby providing a porous material adsorbent, its preparation method and application.

[0004] The first aspect of this invention protects a method for preparing a porous material adsorbent, wherein the preparation method includes the following steps:

[0005] (1) Add ruthenium-containing substances and organic peroxides to a first organic solvent to carry out a first reaction, add a crosslinking agent to carry out a second reaction, and obtain a precursor solution;

[0006] (2) Add a second organic solvent to the precursor solution and mix to obtain a ligand mixture;

[0007] (3) Add graphene oxide to the ligand mixture to obtain an adsorbent slurry. Separate the adsorbent slurry into solid and liquid, calcine, and extrude to obtain a porous material adsorbent.

[0008] According to the present invention, in step (1), the ruthenium-containing substance includes elemental ruthenium and / or ruthenium-containing compounds.

[0009] According to the present invention, the elemental ruthenium includes ruthenium powder (Ru).

[0010] According to the present invention, the ruthenium-containing compound includes ruthenium oxide (RuO2) and / or ruthenium trichloride (RuCl3).

[0011] According to the present invention, the first organic solvent is a conventional organic solvent in the field, such as a chlorinated organic solvent, an aromatic solvent (toluene), an aromatic solvent (diethyl ether), etc., preferably including a chlorinated organic solvent.

[0012] According to the present invention, the chlorine-containing organic solvent includes at least one of chlorobenzene (C6H5Cl), dichlorobenzene (C6H4Cl2), and chloroform (CHCl3).

[0013] According to the present invention, the organic peroxide includes di-tert-butyl peroxide (C8HO2) and dicyclohexyl peroxide dicarbonate (C8HO2). 14 H 22 O6) and benzoyl peroxide (C 14 H 10 At least one of O4).

[0014] According to the present invention, the crosslinking agent includes hydroxyethyl acrylate (C5H8O3) and hydroxypropyl acrylate (C6H... 10 O3) and vinyltriethoxysilane (C8H) 18 At least one of O3Si).

[0015] In this invention, crosslinking improves the strength of the product.

[0016] According to the present invention, the solid-liquid ratio of the ruthenium-containing substance to the first organic solvent is 1:(400-600), with units of g / mL.

[0017] According to the present invention, the ratio of the ruthenium-containing substance, the organic peroxide, and the crosslinking agent is 1g:(2-5)mL:(20-50)mL.

[0018] According to the present invention, the temperature of the first reaction is 20-40°C and the time is 1-3 hours.

[0019] According to the present invention, the temperature of the second reaction is 20-40°C and the time is 0.5-2h.

[0020] According to the present invention, in step (2), the second organic solvent is a conventional organic solvent in the field, such as an alcohol solvent, an aromatic solvent (toluene), an aromatic solvent (diethyl ether), etc., preferably including an alcohol solvent.

[0021] According to the present invention, the alcohol solvent includes at least one of anhydrous ethanol, methanol and isopropanol.

[0022] According to the present invention, the solid-liquid ratio of the ruthenium-containing substance to the second organic solvent is 1:(15-40), with units of g / mL.

[0023] In this invention, the mixing in step (2) is a conventional mixing in the art.

[0024] In this invention, graphene oxide can be commercially available or prepared. The specific steps for preparing graphene oxide include: adding a third organic solvent to graphene, then adding acid under an ice bath to carry out a third reaction, cooling, washing with water, and drying to obtain graphene oxide.

[0025] In this invention, the graphene oxide is in powder form.

[0026] According to the present invention, the third organic solvent includes at least one of benzyl alcohol, glycerol and cyclohexanol.

[0027] According to the present invention, the acid includes at least one of sulfuric acid, nitric acid, and perchloric acid; the concentration of sulfuric acid is 98%, the concentration of nitric acid is 98%, and the concentration of perchloric acid is 72%.

[0028] According to the present invention, the ratio of the amount of graphene, the third organic solvent, and the acid is 1g:(10-20)mL:(1-5)mL.

[0029] In this invention, the ice bath is a conventional ice bath method in the art.

[0030] According to the present invention, the temperature of the third reaction is 0-3°C and the time is 30-45 min.

[0031] According to the present invention, in step (3), the graphene oxide refers to all graphene oxides, and the ligand mixture refers to all ligand mixtures. The amounts are clear and do not need to be further limited.

[0032] According to the present invention, the specific steps of solid-liquid separation include centrifugation, washing, filtration, and drying.

[0033] According to the present invention, the centrifugation time is 20-30 min and the rotation speed is 3600-4000 r / min.

[0034] According to the present invention, the drying temperature is 70-90°C and the time is 4-8 hours.

[0035] According to the present invention, the calcination temperature is 200-300℃ and the time is 1-3h.

[0036] In this invention, extrusion molding is a conventional operation in the field. Typically, without limitation, the specific steps of extrusion molding are dry mixing, adding water, wet mixing, and extrusion.

[0037] A second aspect of this invention protects a porous material adsorbent prepared by the aforementioned preparation method.

[0038] The third aspect of this invention protects the application of the aforementioned porous material adsorbent in the field of adsorption desulfurization.

[0039] The technical solution of this invention has the following advantages:

[0040] This invention provides a method for preparing a porous material adsorbent, wherein the preparation method includes the following steps: (1) adding a ruthenium-containing substance and an organic peroxide to a first organic solvent to carry out a first reaction, adding a crosslinking agent to carry out a second reaction to obtain a precursor liquid; (2) adding a second organic solvent to the precursor liquid and mixing to obtain a ligand mixture; (3) adding graphene oxide to the ligand mixture and mixing to obtain an adsorbent slurry, and performing solid-liquid separation, calcination, and extrusion molding of the adsorbent slurry to obtain a porous material adsorbent. The ligand mixture in the porous material adsorbent prepared by this invention enhances the strength of the material; while graphene oxide has a large theoretical specific surface area and abundant oxygen-containing functional groups. These oxygen-containing functional groups make the connection between graphene oxide and the ligand mixture more compact. The resulting porous material adsorbent has a large specific surface area, large pore size, and large pore volume, and has high compressive strength. When applied to the field of adsorption desulfurization, it has high total sulfur penetration capacity and tail gas outlet accuracy. Attached Figure Description

[0041] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0042] Figure 1 These are electron microscope images of the porous material adsorbent prepared in Example 1. Detailed Implementation

[0043] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0044] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0045] The alumina balls were purchased from Zibo Zhongze New Material Technology Co., Ltd.

[0046] Example 1

[0047] This embodiment provides a method for preparing a porous material adsorbent, comprising the following steps:

[0048] (1) In a sealed container, weigh 10g of ruthenium powder, 20mL of dicyclohexyl peroxide dicarbonate and 4000mL of dichlorobenzene, stir evenly, carry out the first reaction at 20℃ for 1h, add 200mL of vinyltriethoxysilane, carry out the second reaction at 20℃ for 1h, and obtain the precursor solution.

[0049] (2) Add 400 mL of methanol to the precursor solution obtained in step (1) and mix to obtain a ligand mixture;

[0050] (3) Add 100g of graphene to 1000mL of cyclohexanol, add 200mL of sulfuric acid under ice bath, and then carry out the third reaction. The reaction temperature is 0℃ and the time is 30min. After cooling, wash with water and dry to obtain graphene oxide.

[0051] (4) Add all the graphene oxide obtained in step (3) to all the ligand mixture obtained in step (2), mix and stir evenly to obtain an adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 90℃ for 8 h, calcine at 200℃ for 1 h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-1;

[0052] from Figure 1 As shown in the figure, which is an electron microscope image of the porous material adsorbent, uniformly dispersed particles can be observed on the graphene surface, proving that the porous material adsorbent has been successfully prepared. The open surface structure of the porous material adsorbent has a high adsorption capacity.

[0053] Example 2

[0054] This embodiment provides a method for preparing a porous material adsorbent, comprising the following steps:

[0055] (1) In a sealed container, weigh 13g of ruthenium oxide, 52mL of di-tert-butyl peroxide and 6500mL of chlorobenzene, stir evenly, carry out the first reaction at 30℃ for 2h, add 390mL of hydroxypropyl acrylate, carry out the second reaction at 20℃ for 1h, and obtain the precursor solution.

[0056] (2) Add 400 mL of isopropanol to the precursor solution obtained in step (1) and mix to obtain a ligand mixture;

[0057] (3) Add 100g of graphene to 1500mL of glycerol, add 300mL of nitric acid under ice bath, and then carry out the third reaction. The reaction temperature is 0℃ and the time is 30min. After cooling, wash with water and dry to obtain graphene oxide.

[0058] (4) Add all the graphene oxide obtained in step (3) to all the ligand mixture obtained in step (2), mix and stir evenly to obtain adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 70℃ for 5 h, calcine at 300℃ for 2 h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-2.

[0059] Example 3

[0060] This embodiment provides a method for preparing a porous material adsorbent, comprising the following steps:

[0061] (1) In a sealed container, weigh 21g of ruthenium trichloride, 105mL of benzoyl peroxide and 8400mL of chloroform, stir evenly, carry out the first reaction at 40℃ for 3h, add 1050mL of hydroxyethyl acrylate, carry out the second reaction at 40℃ for 1h, and obtain the precursor solution.

[0062] (2) Add 400 mL of anhydrous ethanol to the precursor solution obtained in step (1) and mix to obtain a ligand mixture;

[0063] (3) Add 100g of graphene to 2000mL of benzyl alcohol, add 500mL of perchloric acid in an ice bath, the reaction temperature is 0℃, the reaction time is 30min, after cooling, wash with water and dry to obtain graphene oxide.

[0064] (4) Add all the graphene oxide obtained in step (3) to all the ligand mixture obtained in step (2), mix and stir evenly to obtain adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 80℃ for 4 h, calcine at 200℃ for 3 h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-3.

[0065] Example 4

[0066] This embodiment provides a method for preparing a porous material adsorbent, comprising the following steps:

[0067] (1) In a sealed container, weigh 13g of ruthenium oxide, 39mL of benzoyl peroxide and 5200mL of chloroform, stir evenly and carry out the first reaction at 30℃ for 2.5h. Add 390mL of vinyltriethoxysilane and carry out the second reaction at 40℃ for 2h to obtain the precursor solution.

[0068] (2) Add 400 mL of anhydrous ethanol to the precursor solution obtained in step (1) and mix to obtain a ligand mixture;

[0069] (3) Add 100g of graphene to 1500mL of benzyl alcohol, add 300mL of perchloric acid in an ice bath, the reaction temperature is 0℃, the time is 30min, after cooling, wash with water and dry to obtain graphene oxide.

[0070] (4) Add all the graphene oxide obtained in step (3) to all the ligand mixture obtained in step (2), mix and stir evenly to obtain adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 70℃ for 8 h, calcine at 300℃ for 2 h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-4.

[0071] Example 5

[0072] This embodiment provides a method for preparing a porous material adsorbent, comprising the following steps:

[0073] (1) In a sealed container, weigh 21g of ruthenium trichloride, 42mL of di-tert-butyl peroxide and 8400mL of dichlorobenzene, stir evenly, carry out the first reaction at 40℃ for 3h, add 1050mL of hydroxypropyl acrylate, carry out the second reaction at 20℃ for 2h, and obtain the precursor solution.

[0074] (2) Add 400 mL of methanol to the precursor solution obtained in step (1) and mix to obtain a ligand mixture;

[0075] (3) Add 100g of graphene to 1000mL of cyclohexanol, add 500mL of sulfuric acid under ice bath, and then carry out the third reaction. The reaction temperature is 0℃ and the time is 30min. After cooling, wash with water and dry to obtain graphene oxide.

[0076] (4) Add all the graphene oxide obtained in step (3) to all the ligand mixture obtained in step (2), mix and stir evenly to obtain adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 80℃ for 6 h, calcine at 200℃ for 1 h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-5.

[0077] Example 6

[0078] This embodiment provides a method for preparing a porous material adsorbent, comprising the following steps:

[0079] (1) In a sealed container, weigh 10g of ruthenium powder, 50mL of dicyclohexyl peroxide and 5000mL of chlorobenzene, stir evenly, carry out the first reaction at 30℃ for 3h, add 500mL of hydroxyethyl acrylate, carry out the second reaction at 40℃ for 2h, and obtain the precursor solution.

[0080] (2) Add 400 mL of isopropanol to the precursor solution obtained in step (1) and mix to obtain a ligand mixture;

[0081] (3) Add 100g of graphene to 2000mL of glycerol, add 200mL of nitric acid in an ice bath, the reaction temperature is 0℃, the reaction time is 30min, after cooling, wash with water and dry to obtain graphene oxide.

[0082] (4) Add all the graphene oxide obtained in step (3) to all the ligand mixture obtained in step (2), mix and stir evenly to obtain adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 90℃ for 4 h, calcine at 300℃ for 2 h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-6.

[0083] Example 7

[0084] This embodiment provides a method for preparing a porous material adsorbent, comprising the following steps:

[0085] (1) In a closed container, the method of Example 1 is followed, except that "weighing 10g of ruthenium powder, 20mL of dicyclohexyl peroxide, and 4000mL of dichlorobenzene" is used instead of "weighing 10g of ruthenium powder, 20mL of dicyclohexyl peroxide, and 4000mL of dichlorobenzene".

[0086] Steps (2), (3), and (4) are performed in accordance with the method of Example 1 to obtain porous material adsorbent-7.

[0087] Comparative Example 1

[0088] This comparative example provides a method for preparing a porous material adsorbent, comprising the following steps:

[0089] (1) In a sealed container, weigh 13g of ruthenium oxide, 39mL of benzoyl peroxide and 5200mL of chloroform, stir evenly, carry out the first reaction at 20℃ for 2h, add 390mL of vinyltriethoxysilane, carry out the second reaction at 40℃ for 2h, and obtain the precursor solution.

[0090] (2) Add 400 mL of anhydrous ethanol to the precursor solution obtained in step (1) and mix to obtain a ligand mixture;

[0091] (3) Add 100g of alumina balls to all the ligand mixtures obtained in step (2), mix and stir evenly to obtain an adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600r / min for 30min, wash, filter, dry at 70℃ for 8h, calcine at 300℃ for 2h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-D1.

[0092] Comparative Example 2

[0093] This comparative example provides a method for preparing a porous material adsorbent, comprising the following steps:

[0094] (1) In a sealed container, 100g of graphene was added to 1000mL of cyclohexanol. Under ice bath conditions, 200mL of sulfuric acid was added and the reaction was carried out at 0℃ for 30min. After cooling, the mixture was washed with water and dried to obtain graphene oxide.

[0095] (2) Add all the graphene oxide obtained in step (1) to 400 mL of methanol, mix and stir evenly to obtain an adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 90℃ for 8 h, calcine at 200℃ for 1 h, dry mix the calcined material, add water, wet mix and extrude to obtain porous material adsorbent-D2.

[0096] Comparative Example 3

[0097] This comparative example provides a method for preparing a porous material adsorbent, comprising the following steps:

[0098] (1) In a closed container, weigh 10g of ruthenium powder, 20mL of dicyclohexyl peroxide and 4000mL of dichlorobenzene, stir evenly and react at 40℃ for 2h to obtain the precursor solution.

[0099] Steps (2), (3), and (4) are performed in accordance with the method of Example 1 to obtain porous material adsorbent-D3.

[0100] Comparative Example 4

[0101] This comparative example provides a method for preparing a porous material adsorbent, comprising the following steps:

[0102] Steps (1) and (2) are performed in accordance with the method of Example 1.

[0103] (3) Add the same amount of graphene as in Example 1 to all the ligand mixtures obtained in step (2), mix and stir evenly to obtain an adsorbent slurry; centrifuge the obtained adsorbent slurry at 3600 r / min for 30 min, wash, filter, dry at 90℃ for 8 h, calcine at 200℃ for 1 h, dry mix the calcined material, add water, wet mix, and extrude to obtain porous material adsorbent-D4.

[0104] Test Example 1

[0105] The prepared porous material adsorbent was characterized using a physical adsorption instrument (model ASAP2460, Micron Instruments, USA), and its specific surface area, pore volume, and pore size were measured.

[0106] The porous material adsorbent was characterized using a particle strength tester (model HB-KQD, Haibo Instruments Co., Ltd.). The compressive strength test involved placing the sample on a lifting platform and rotating the handle to raise the platform. Once the sample contacted the lower end of a spring balance, it was compressed, and the magnitude of the pressure was indicated by the pressure gauge. When the sample began to break, the pressure gauge pointer suddenly reversed; this value was the compressive strength of the sample. The test was repeated 20 times, and the average value was taken. The specific test results are shown in Table 1.

[0107] Table 1

[0108] <![CDATA[Specific surface area (m 2 / g)]]> <![CDATA[Pore volume (cm 3 / g)]]> Aperture (nm) <![CDATA[Compressive strength (N / cm -1 )]]> Example 1 1516.15 0.96 4.48 126.33 Example 2 1463.65 0.94 4.47 116.23 Example 3 1654.65 1.08 4.93 113.69 Example 4 1865.26 1.38 5.64 126.34 Example 5 1671.23 1.19 5.55 121.23 Example 6 1538.33 0.98 4.58 134.34 Example 7 1401.23 0.83 4.35 109.64 Comparative Example 1 765.36 0.46 2.78 103.61 Comparative Example 2 657.64 0.34 2.16 106.54 Comparative Example 3 468.25 0.23 2.02 101.38 Comparative Example 4 536.32 0.28 2.12 96.32

[0109] Test Example 2

[0110] Porous material adsorbents were used as desulfurizing agents, and their desulfurization effect (outlet accuracy and breakthrough sulfur capacity) was evaluated by testing. The outlet accuracy test is the sulfur content in the exhaust gas, and the breakthrough sulfur capacity is the desulfurization performance after the test.

[0111] Test conditions:

[0112] Reaction tube specifications: 100mm long, 5.5mm inner diameter hard glass tube; Adsorbent loading: 1mL (particle size 80-160 mesh); Pressure: atmospheric pressure; Temperature: room temperature; Space velocity: 3000h⁻¹ -1 Raw material gas: hydrogen sulfide 500ppm, methanethiol 100ppm, ethanethiol 100ppm, carbonyl sulfide 100ppm, dimethyl sulfide 100ppm, tetrahydrothiophene 100ppm, nitrogen balances the raw material gas.

[0113] The calculation method for the exhaust gas outlet accuracy is as follows: using an Agilent gas chromatograph, the instrument's testing accuracy is 10 ppb.

[0114] Total sulfur penetration capacity at a gas hourly space velocity of 1750 h⁻¹ -1The percentage by weight of sulfur that the adsorbent can absorb while ensuring the process purification index (removal rate reduced to 99%) under the condition of reaction temperature of 120℃.

[0115] The method for calculating the total sulfur breakthrough capacity is as follows: the sulfur capacity is determined by combustion neutralization method. The specific method is as follows: after the sulfur-absorbing sample is ground, 0.1g of the ground sample is weighed and placed evenly in a porcelain boat. The porcelain boat is placed in the middle of a quartz tube. Under the condition of oxygen introduction, the tail gas is absorbed with hydrogen peroxide with a concentration of 3wt%. After the reaction is completed, it is titrated with sodium hydroxide standard solution.

[0116]

[0117] The concentration of c-sodium hydroxide standard solution, mol / L;

[0118] V - Volume of sodium hydroxide standard solution consumed in the titration, mL;

[0119] m - Mass of the sample, in g;

[0120] The molar mass of M-sulfur(1 / 2S) is expressed in g / mol, [M(1 / 2S) = 16.03].

[0121] The evaluation preparation of the porous material adsorbent: Weigh 200g of the porous material adsorbent prepared in the examples and comparative examples, grind and sieve it to obtain 80-160 mesh samples for use. The specific test results are shown in Table 2.

[0122] Table 2

[0123]

[0124]

[0125] The porous material adsorbent prepared by this invention has a large specific surface area, large pore size and large pore volume, and high compressive strength. When applied to the field of adsorption desulfurization, it has a high total sulfur penetration capacity and tail gas outlet accuracy.

[0126] A comparison of Example 1 and Example 7 shows that the specific amounts of ruthenium-containing substances, organic peroxides, and crosslinking agents can further optimize the structural characteristics, mechanical properties, and adsorption performance of the prepared porous material adsorbent.

[0127] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing an adsorbent for desulfurization porous materials, characterized in that, The preparation method includes the following steps: (1) Add ruthenium-containing substances and organic peroxides to the first organic solvent to carry out the first reaction, add crosslinking agent to carry out the second reaction, and obtain the precursor solution; (2) Add a second organic solvent to the precursor solution and mix to obtain a ligand mixture; (3) Add graphene oxide to the ligand mixture and mix to obtain an adsorbent slurry. Separate the adsorbent slurry into solid and liquid, calcine and extrude it to obtain a porous material adsorbent. The organic peroxide includes at least one of di-tert-butyl peroxide, dicyclohexyl peroxydicarbonate, and benzoyl peroxide; The crosslinking agent includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, and vinyltriethoxysilane; The ratio of the ruthenium-containing substance, the organic peroxide, and the crosslinking agent is 1g:(2-5)mL:(20-50)mL; The temperature of the first reaction is 20-40℃, and the time is 1-3 hours; The second reaction is carried out at a temperature of 20-40℃ for a time of 0.5-2 hours. The roasting temperature is 200-300℃ and the time is 1-3h.

2. The preparation method according to claim 1, characterized in that, In step (1), the ruthenium-containing substance includes elemental ruthenium and / or ruthenium-containing compounds; And / or, the first organic solvent includes at least one of chlorinated organic solvents, aromatic solvents, and ether solvents.

3. The preparation method according to claim 2, characterized in that, The elemental ruthenium includes ruthenium powder; And / or, the ruthenium-containing compound includes ruthenium oxide and / or ruthenium trichloride; And / or, the first organic solvent is a chlorinated organic solvent.

4. The preparation method according to claim 3, characterized in that, The chlorinated organic solvent includes at least one of chlorobenzene, dichlorobenzene, and trichloromethane.

5. The preparation method according to claim 1, characterized in that, The solid-liquid ratio of the ruthenium-containing substance to the first organic solvent is 1:(400-600), with units of g / mL.

6. The preparation method according to claim 1, characterized in that, In step (2), the second organic solvent includes at least one of alcohol solvents, aromatic solvents, and ether solvents.

7. The preparation method according to claim 6, characterized in that, The second organic solvent is an alcohol solvent.

8. The preparation method according to claim 7, characterized in that, The alcohol solvent includes at least one of anhydrous ethanol, methanol, and isopropanol.

9. The preparation method according to claim 1, characterized in that, The solid-liquid ratio of the ruthenium-containing substance to the second organic solvent is 1:(15-40), with units of g / mL.

10. The preparation method according to claim 1, characterized in that, The specific steps of the solid-liquid separation include centrifugation, washing, filtration, and drying.

11. The preparation method according to claim 10, characterized in that, The centrifugation time is 20-30 min, and the rotation speed is 3600-4000 r / min; And / or, the drying temperature is 70-90℃ and the time is 4-8h.

12. An adsorbent for desulfurization porous materials prepared by the preparation method according to any one of claims 1-11.

13. The application of the porous adsorbent for adsorption desulfurization as described in claim 12 in the field of adsorption desulfurization.

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